Molding packaging material and battery case

ABSTRACT

Provided is a molding packaging material that can have an increased use life, can suppress a decrease over time in inter-layer lamination strength, and can have superior molding properties in extrusion molding, draw forming, and the like. The laminate molding packaging material contains: an outside substrate layer ( 2 ) comprising a heat resistant resin; an inside sealant layer ( 3 ) comprising a thermoplastic resin; and a metal foil provided between the two layers as a barrier layer ( 4 ). A matte coat layer ( 6 ) comprising a heat resistant resin coating film containing a dispersion of inorganic or organic solid microparticles is formed on the outer surface of the outside substrate layer ( 2 ), and the gloss value of the surface thereof is suppressed to no greater than 30%.

TECHNICAL FIELD

The present invention relates to a laminate molding packaging materialwhich is molded into a tray shape by draw forming or bulging to be used.More specifically, the present invention relates to a laminate packagingmaterial which is suitably used as a case material of secondarybatteries, such as lithium ion batteries for notebook personalcomputers, cellular phones, and on-vehicle and fixed type power sources,and further is suitably used also as a packaging material for foods,pharmaceuticals, and the like.

TECHNICAL BACKGROUND

Heretofore, as packaging materials for foods, such as retort foods,pharmaceuticals, or industrial chemicals, a laminate packaging materialwhich contains a metallic foil excellent in barrier properties of oxygenor moisture and in which the metallic foil is laminated between asubstrate film and a sealant layer in order to prevent the chemicalchange, degradation, decomposition, and the like of contents has beenwidely used (Patent Document 1).

On the other hand, in recent years, in connection with a reduction inthe size and the weight of various electronic devices, such as OAdevices (e.g., personal computers), cellular phones, game machines,headphone stereos, and electronic notebooks, a lithium ion polymersecondary batteries has been increasingly used from the viewpoint ofachieving a reduction in the size and the weight also as a battery of apower source portion in many cases. In the lithium ion polymer secondarybattery, when an electrolytic solution in the battery reacts with waterand then hydrofluoric acid is generated, a reduction in the performanceof the battery is caused or liquid leakage occurs by corrosion of thecase. Therefore, the same laminate packaging material as above havingexcellent water vapor barrier properties and high sealing properties hasbeen increasingly used as a material for use in the case (storing case).

More specifically, as the case material of the lithium ion polymersecondary battery (packaging material), a laminate packaging material inwhich an outer layer containing a heat-resistant resin film of apolyester type, an epoxy type, an acrylic type, or the like, anintermediate layer mainly containing an aluminum foil as a water vaporbarrier layer, and an inside sealant layer containing a heat adhesivepolyolefin resin for sealing a polymer electrolyte which is the contentare laminated in order and integrated has been used (Patent Documents 2and 3).

The laminate packaging material for battery case described above ismolded into a three-dimensional rectangular parallelepiped shape or thelike by bulging or deep draw forming in order to increase the capacityas much as possible to charge a polymer electrolyte, and then used as abattery case in many cases.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Unexamined Patent Application PublicationNo. 2004-319414

Patent Document 2: Japanese Unexamined Patent Application PublicationNo. 2001-202928

Patent Document 3: Japanese Unexamined Patent Application PublicationNo. 2001-266810

SUMMARY OF INVENTION Problems to be Solved by the Invention

However, in the above-described known laminate packaging materials, themolding properties when molded into a tray shape are generally poor andthere is a possibility such that cracks and pinholes are generated bybulging or draw forming. Therefore, the laminate packaging materialshave had a disadvantage in that the laminate packaging materials aredifficult to be molded into a desired depth with sufficiently highcapacity.

Moreover, in most of the above-described known laminate packagingmaterials, since the aluminum foil as a barrier layer and the insidesealant layer are bonded using a two component mixed adhesive in which amain agent having a common hydroxyl group and a curing agent having anisocyanate group are mixed, the lamination strength between the aluminumfoil and the sealant layer decreases with time due to an electrolyticsolution which is the content, and consequently the electrolyticsolution which is the content may leak. Therefore, there has been aproblem in that a desired increase in life has not been achieved.

The present invention has been made in view of the technical backgrounddescribed above. It is a first object of the invention to provide amolding packaging material whose molding properties are improved andwhich can achieve molding with sharpness and a high depth withoutgenerating cracks and pinholes.

In addition, it is another object of the present invention to provide amolding packaging material in which a reduction in the interlayerlamination strength caused by an influence of an electrolytic solutioncan be prevented and a reduction in the interlayer lamination strengthcaused by an influence of a generation of heat and an expansion and acontraction of the packaging material due to a repetition of charge anddischarge can be prevented, so that the interlayer lamination strengthis excellent, to prevent causing poor appearance even when anelectrolytic solution adheres to the surface, and further to provide amanufacturing method capable of manufacturing such a molding packagingmaterial with good productivity.

The other purposes and advantages of the present invention are clarifiedfrom a description of preferable embodiments described below.

Means for Solving the Problems

In order to achieve the objects, the present invention provides thefollowing measures.

[1] A molding packaging material, containing an outside substrate layercontaining a heat-resistant resin, an inside sealant layer containing athermoplastic resin, and a metallic foil as a barrier layer providedbetween the layers, in which a matte coat layer containing aheat-resistant resin composition containing a dispersion of inorganicand/or organic solid fine particles is formed by coating on the outsidesurface of the outside substrate layer and the gloss value of thesurface on the side of the matte coat layer is set to 30% or lower.

[2] A molding packaging material, containing an outside substrate layercontaining a heat-resistant resin, an inside sealant layer containing athermoplastic resin, and a metallic foil as a barrier layer providedbetween the layers, in which at least an inside surface of the metallicfoil layer is subjected to chemical conversion treatment, an insideadhesion resin layer having adhesiveness to both the metallic foil asthe barrier layer and the resin of the inside sealant layer is laminatedon the chemical conversion-treated surface, the inside sealant layer isfurther laminated through the adhesion resin layer,

the outside substrate layer contains a biaxially oriented polyamideresin film, a matte coat layer containing a resin composition containinga dispersion of inorganic and/or organic solid fine particles in aheat-resistant resin component is formed by coating on the outsidesurface of the outside substrate layer, and the gloss value of thesurface on the side of the matte coat layer is set to 30% or lower.

[3] The molding packaging material described in [1] or [2] above, inwhich the gloss value is 1% to 15%.

[4] The molding packaging material described in any one of [1] to [3]above, in which the heat-resistant resin composition of the matte coatlayer contains a heat-resistant resin in which fluorine is added to theskeleton of a main agent as the main component.

[5] The molding packaging material described in [4] above, in which theheat-resistant resin composition of the matte coat layer contains a twocomponent curing type heat-resistant resin containing a copolymer oftetrafluoroolefin and carboxylic acid vinyl ester as the main component.

[6] The molding packaging material described in [5] above, in which theheat-resistant resin composition of the matte coat layer furthercontains a urethane resin and/or an acrylic resin.

[7] The molding packaging material described in any one of [1] to [6]above, in which, in the heat-resistant resin composition of the mattecoat layer, 0.1 to 60 wt % of a dispersion of inorganic and/or organicsolid fine particles having an average particle diameter of 1 μm to 10μm is contained in the heat-resistant resin component.

[8] The molding packaging material described in any one of [1] to [7]above, in which the inside sealant layer contains a propylenehomopolymer or a copolymer containing at least propylene and ethylene asa copolymerization component.

[9] The molding packaging material described in [8] above, in which theinside sealant layer is a polymer or a copolymer having a melting pointof 130° C. to 160° C. and an MFR of 1 to 25 g/10 min.

[10] The molding packaging material described in any one of [2] to [9]above, in which the inside adhesion resin layer contains an adhesivecontaining a polyolefin resin having a carboxyl group and amultifunctional isocyanate compound.

[11] The molding packaging material described in [10] above, in which anequivalent ratio [NCO]/[OH] of an isocyanate group of themultifunctional isocyanate compound to a hydroxyl group constituting thecarboxyl group of the polyolefin resin is 1.0 to 10.0.

[12] The molding packaging material described in [10] or [11] above, inwhich, in the polyolefin resin having a carboxyl group, the melt flowrate (MFR) measured at 130° C. is 5 to 40 g/10 min.

[13] A battery case, which is obtained by performing deep draw formingor bulging of the molding packaging material described in any one of [1]to [12] above.

[14] The molding packaging material described in any one of [1] to [12]above, which is used as a packaging material for foods orpharmaceuticals.

[15] A method for manufacturing a molding packaging material, includinga process of subjecting at least one surface of a metallic foil for abarrier layer to chemical conversion treatment, a process of bonding abiaxially oriented polyamide film to the other surface of the metallicfoil with an outside adhesive to form an outside substrate layer, aprocess of applying a resin composition in which 0.1 to 60 wt % of adispersion of inorganic and/or organic solid fine particles having anaverage particle diameter of 1 μm to 10 μm is contained in a twocomponent curing type heat-resistant resin containing a copolymer oftetrafluoroolefin and carboxylic acid vinyl ester to the surface of theoutside substrate layer, and then drying to form a matte coat layerwhose gloss value is controlled to be 1 to 30%, a process of forming aninside adhesion resin layer having adhesiveness to both the metallicfoil as the barrier layer and a resin of an inside sealant layerdescribed later on one chemical conversion-treated surface of themetallic foil, a process of laminating and forming the sealant layercontaining a thermoplastic resin on the inside adhesion resin layer, anda process of heat treating a laminate obtained by the processes abovewith a heat roll heated to 130° C. to 220° C. in such a manner that theoutside substrate layer is on the side of the heat roll.

[16] The method for manufacturing a molding packaging material describedin [15] above, in which a resin containing a propylene homopolymer or acopolymer resin containing at least propylene and ethylene as acopolymerization component and having a melting point of 130° C. to 160°C. and an MFR of 1 to 25 g/10 min is used as the thermoplastic resin ofthe sealant layer.

[17] The method for manufacturing a molding packaging material describedin [15] or [16] above, in which the inside adhesion resin layer isformed by applying and drying an adhesion resin containing a polyolefinresin having a carboxyl group and a multifunctional isocyanate compoundand having an equivalent ratio [NCO]/[OH] of an isocyanate group of themultifunctional isocyanate compound to a hydroxyl group constituting thecarboxyl group of the polyolefin resin of 1.0 to 10.0.

Effects of the Invention

According to the invention of [1] above, due to the fact that the mattecoat layer containing a heat-resistant resin composition containing adispersion of inorganic and/or organic solid fine particles is formed onthe outside surface of the outside substrate layer containing aheat-resistant resin and the gloss value of the surface is controlled to30% or lower, favorable slipping properties are imparted to the surfaceof the packaging material. More specifically, when the gloss valueexceeds 30%, the surface roughness becomes small and the surfaceslipping properties are reduced. Therefore, when the gloss value is setto a value equal to or lower than the value, the packaging materialexcellent in molding properties which is the initial purpose of thepresent invention can be provided. The, gloss value is a value measuredat an incident angle of 60° according to JISK7105.

According to the invention of [2], the molding packaging materialcontains the outside substrate layer, the inside sealant layer, and themetallic foil layer provided between these layers, in which at least aninside surface of the metallic foil is subjected to chemical conversiontreatment and an adhesion resin layer having adhesiveness to both themetallic foil and the resin of the inside sealant layer is laminated onthe chemical conversion-treated surface, and therefore the interlayerlamination strength of the sealant layer and the metallic foil layer canbe sufficiently secured. Moreover, since the outside substrate layer isa biaxially oriented polyamide film, molding packaging material isexcellent in molding properties. Furthermore, a heat-resistant resincomposition containing a dispersion of inorganic and/or organic solidfine particles is applied to the surface, so that the matte coat layerwhose surface gloss value is 30% or lower is formed thereon, andtherefore the surface slipping properties are good, the moldingproperties are excellent, and the appearance is not impaired even whenan electrolytic solution adheres. When the molding packaging material isused as a battery case, for example, a reduction in the interlayerlamination strength of the barrier layer of the metallic foil and theinside sealant layer caused by an influence of an electrolytic solutioncan be prevented and a reduction in the interlayer lamination strengthcaused by an influence of a generation of heat and an expansion and acontraction of the packaging material due to a repetition of charge anddischarge can also be prevented, so that sufficient sealing performancecan be secured. Furthermore, since at least one surface of the metallicfoil layer is subjected to the chemical conversion treatment, acorrosion of the surface of the metallic foil caused by contents (anelectrolytic solution of a battery, foods, pharmaceuticals, and thelike) can be sufficiently prevented.

According to the invention of [3], since the gloss value of the outsidesurface of the packaging material by the formation of the matte coatlayer is set to 1 to 15%, a problem in the appearance which may occurwhen the gloss value is lower than 1%, i.e., a problem such thatirregularities of the surface become excessively large, so that thepackaging material becomes slightly undesirable in the appearance, canbe avoided and further an improvement effect of the molding propertiesobtained due to the fact that the gloss value is 15% or lower can befavorably and stably achieved.

According to the invention of [4], due to the fact that theheat-resistant resin composition of the matte coat layer contains theheat-resistant resin in which fluorine is added to the skeleton of themain agent as the main component, it is a matter of course that thesurface slipping properties can be made more favorable and the moldingproperties can be improved, and further the packaging material whosesurface antifouling property can be improved, so that even when anelectrolytic solution or the like adheres, the appearance may not benoticeably impaired is provided.

According to the invention of [5], due to the fact that the twocomponent curing type heat-resistant resin containing the copolymer oftetrafluoroolefin and carboxylic acid vinyl ester is selected as theheat-resistant resin to which fluorine is added, an improvement effectof the molding properties by imparting the surface slipping propertiesand a prevention effect of appearance degradation due to adhesion of anelectrolytic solution can be more certainly and favorably achieved.

According to the invention of [6], due to the fact that a urethane resinand/or an acrylic resin is further contained in the heat-resistant resinof the invention of [5] above, the strength of the matte coat layer isincreased and also good molding properties can also be imparted toitself.

According to the invention of [7], since inorganic and/or organic solidfine particles having an average particle diameter of 1 to 10 μm areused as a control material of the surface gloss value of the matte coatlayer and a dispersion thereof is contained in the heat-resistant resincomponent in the range of 0.1 to 60 wt %, the gloss value of the mattecoat layer can be easily controlled to 30% or lower and preferably 1 to15% or lower.

According to the invention of [8], since the sealant layer is formedwith a propylene homopolymer or a copolymer resin containing at leastpropylene and ethylene as a copolymerization component, sufficient heatresistance can be secured and excellent sealing performance can besecured.

According to the invention of [9], since the melting point of thepolymer or the copolymer of the invention of [8] above is 130 to 160° C.and the MFR thereof is 1 to 25 g/10 min, sufficient heat resistance canbe secured and moderate fluidity can be realized in sealing, so thatexcellent sealing performance can be secured.

According to the invention of [10], due to the fact that the insideadhesion resin layer is an adhesive containing a polyolefin resin havinga carboxyl group and a multifunctional isocyanate compound, a reductionwith time in the lamination strength between the metallic foil and theinside sealant layer caused by an influence of an electrolytic solutionin the use as a battery case can be effectively reduced and prevented.

According to the invention of [11], since the equivalent ratio[NCO]/[OH] of an isocyanate group of the multifunctional isocyanatecompound to a hydroxyl group constituting a carboxyl group of thepolyolefin resin in the adhesive is 1.0 to 10.0, the packaging materialfor battery case in which the interlayer adhesion strength hardlydecreases over a longer period of time and the useful life is long isprovided.

According to the invention of [12], since the melt flow rate measured at130° C. of the olefin resin having a carboxyl group is 5 to 40 g/10 min,the packaging material in which the useful life is longer in the use asthe packaging material for battery case can be provided.

According to the invention of [13], a battery case which has highinterlayer lamination strength without molding defects is provided.

According to the invention of [14], a food packaging material or apharmaceutical packaging material having high interlayer laminationstrength is provided.

According to the invention of [15], the method for manufacturing amolding packaging material, includes the process of subjecting at leastone surface of a metallic foil for a barrier layer to chemicalconversion treatment, the process of bonding a biaxially orientedpolyamide film to the other surface of the metallic foil with an outsideadhesive to form an outside substrate layer, the process of applying aresin composition in which 0.1 wt % to 60 wt % of a dispersion ofinorganic and/or organic solid fine particles having an average particlediameter of 1 μm to 10 μm is contained in a two component curing typeheat-resistant resin containing a copolymer of tetrafluoroolefin andcarboxylic acid vinyl ester to the surface of the outside substratelayer, and then drying to form a matte coat layer whose gloss value ofthe surface is controlled to be 1 to 30%, the process of forming aninside adhesion resin layer having adhesiveness to both the metallicfoil as the barrier layer and a resin of an inside sealant layerdescribed later on one chemical conversion-treated surface of themetallic foil, the process of laminating and forming the sealant layercontaining a thermoplastic resin on the inside adhesion resin layer, andthe process of heat treating a laminate obtained by the processes abovewith a heat roll heated to 130° C. to 220° C. in such a manner that theoutside substrate layer is on the side of the heat roll. Therefore, itis a matter of course that the molding packaging material having variouseffects described above can be efficiently manufactured, and further themolding packaging material having sufficient lamination strength betweenthe layers of the metallic foil and the polypropylene layer can beprovided.

Therefore, when the obtained molding packaging material is molded into abattery case, for example, a reduction in the interlayer laminationstrength caused by an influence of an electrolytic solution can beprevented and a reduction in the interlayer lamination strength causedby an influence of a generation of heat and an expansion and acontraction of the packaging material due to a repetition of charge anddischarge can also be prevented and sufficient sealing performance canbe secured. Moreover, since at least a surface to which a treatmentliquid is applied of the metallic foil layer of a barrier layer issubjected to the chemical conversion treatment, the molding packagingmaterial can be manufactured in which a corrosion of the surface of themetallic foil caused by contents (an electrolytic solution of a battery,foods, pharmaceuticals, and the like) can be sufficiently prevented.Furthermore, since the matte coat layer containing a specificheat-resistant resin composition containing a dispersion of solid fineparticles, such as silica, and having a surface gloss value of 1 to 30%is provided on the surface of the outside substrate layer containing aheat-resistant resin, the packaging material on the surface of whichmoderate irregularities are formed, to which good slipping propertiesare imparted, and which is excellent also in molding properties can beobtained.

According to the invention of [16], since a propylene homopolymer or apolymer or a copolymer resin containing at least propylene and ethyleneas a copolymerization component and having a melting point of 130° C. to160° C. and an MFR of 1 g/10 min to 15 g/10 min is used as thethermoplastic resin of the inside sealant layer, a molding packagingmaterial which has sufficient heat resistance and in which moderatefluidity can be realized in sealing, so that excellent sealingperformance can be secured can be manufactured.

According to the invention of [17], since the inside adhesion resinlayer is formed by applying and drying an adhesion resin containing apolyolefin resin having a carboxyl group and a multifunctionalisocyanate compound and having an equivalent ratio [NCO]/[OH] of anisocyanate group of the multifunctional isocyanate compound to ahydroxyl group constituting the carboxyl group of the polyolefin resinof 1.0 to 10.0, a reduction with time in the adhesion strength betweenthe metallic foil and the inside sealant layer by the electrolyticsolution of the battery is sufficiently suppressed over a long period oftime. Therefore, excellent electrolytic solution resistance is impartedand moreover the moisture penetration amount is small, and thus a stablepackaging material for battery case with long life can be manufactured.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross sectional view illustrating one embodiment of amolding packaging material according to the present invention.

FIG. 2 is a schematic explanatory view illustrating a method formanufacturing a molding packaging material according to the presentinvention.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

One preferable embodiment of a molding packaging material 1 according tothe invention is illustrated in FIG. 1. The molding packaging material(1) is molded into an approximately rectangular parallelepiped shapewhose upper surface is made to open, for example, to be used as a caseof a lithium ion polymer secondary battery.

In the molding packaging material (1), an outside substrate layer (2)containing a heat-resistant resin film is laminated and integrated onone surface of a metallic foil (4) as a barrier layer through anadhesive layer (11) and also a two component curing type resincomposition containing a dispersion of inorganic and/or organic solidfine particles in a heat-resistant resin component is applied to theoutside surface of the outside substrate layer (2), i.e., a surface (2a) on the side opposite to the metallic foil, whereby and thus the mattecoat layer (6) is formed. An inside sealant layer (3) containing apolypropylene resin is laminated and integrated on another surface (4 a)of the metallic foil (4) through an inside adhesion resin layer (5)having adhesiveness to both the metallic foil (4) and the interfaceresin of an inside sealant layer (3).

The outside substrate layer (2) may have a single layer configurationcontaining a specific heat-resistant resin or a multilayer configurationcontaining various kinds of heat-resistant resin different in the typeand the properties.

Similarly, the inside sealant layer (3) may be one having a heatadhesive resin layer containing polypropylene for at least the innermostlayer, and another intermediate resin layer may be interposed betweenthe inside adhesion resin layer (5) and the innermost layer of theinside sealant layer (3). In this case, the intermediate resin layerinterposed therebetween is regarded as a part of the sealant layer (3)in the invention. The inside adhesion resin layer (5) may be a singlecomposition of a polypropylene resin having a carboxyl group, forexample, or a mixed composition of two or more kinds of substancesdifferent in the melting point.

(Outside Substrate Layer)

The outside substrate layer (2) containing a heat-resistant resin bearsstrength and good molding properties as a packaging material. Althoughnot particularly limited, polyamide resin, such as 6 nylon, 66 nylon,and MXD nylon, or polyester resin is suitably used. Among the above, abiaxially oriented polyamide resin film, particularly 6 nylon, ispreferably used. The heat-resistant resin film layer may be used as asingle layer or two or more kinds thereof may be laminated for use. Thethickness of the outside substrate layer (2) is preferably set to 12 to50 μm and preferably about 15 to 30 μm. Due to the fact that thethickness is set to be equal to or higher than the preferable lowerlimit, sufficient strength as a packaging material can be secured andalso due to the fact that the thickness is set to be equal to or lowerthan the preferable upper limit, stress in bulging and draw forming canbe made small, so that the molding properties can be improved.

(Matte Coat Layer)

The matte coat layer (6) has a main function for improving the moldingproperties and preventing the appearance from being impaired due toadhesion of an electrolytic solution in the invention and is formed byapplying a treatment liquid containing a resin composition containing adispersion of inorganic and/or organic solid fine particles in aheat-resistant resin component, and then drying. By the formation of thematte coat layer (6), the gloss value of the outside surface of thepackaging material (1) is controlled to about 30% or lower, particularlypreferably 1 to 15%, and still more preferably 2 to 10%.

When the gloss value exceeds 30%, the improvement effect of the moldingproperties is poor. However, even when the gloss value is set to lowerthan 1%, there is no merit due to an improvement of the effect and, onthe contrary, demerits, such as degradation of the surface appearanceand an increase in cost, are noticeable.

The heat-resistant resin for use in the matte coat layer (6) is notparticularly limited and one containing polyol as a main agent andmultifunctional isocyanate as a curing agent is generally used. Inparticular, a heat-resistant resin in which fluorine is added to theskeleton of the main agent, such as a two component curing typeheat-resistant resin, e.g., a copolymer of tetrafluoroolefin andcarboxylic acid vinyl ester, a copolymer of tetrafluoroolefin and alkylvinyl ether, a copolymer of chlorotrifluoroolefin and carboxylic acidvinyl ester, and a copolymer of chlorotrifluoroolefin and alkyl vinylether, can be used. Among the above, the copolymer of tetrafluoroolefinand carboxylic acid vinyl ester can be suitably used. By the use of theheat-resistant resin containing these fluorine components as a matrixcomponent, the slipping properties of the surface of the matte coatlayer (6) are further improved and more excellent antifouling propertycan be imparted. By adding a urethane resin and/or an acrylic resin tothe fluorine containing resin, a further improvement of strength andmolding properties may be achieved.

On the other hand, as the dispersion of solid fine particles containedin the resin component of the matte coat layer (6), not only inorganicparticles but also organic particles can be used. The particles may bemixed. Herein, as the inorganic particles, one or two or more of silica,alumina, calcium oxide, calcium carbonate, calcium sulfate, calciumsilicate, carbon black, and the like can be used, and, among the above,the use of silica is preferable. As the organic particles, fineparticles of an acrylic acid ester compound, a polystyrene compound, anepoxy resin, a polyamide compound, crosslinked substances thereof, andthe like can be used.

As the fine particles, one having an average particle diameter of 1 μmto 10 μm as the particle diameter is preferably used and particularlyone having an average particle diameter of 2 μm to 5 μm is preferable.When fine particles having a particle diameter having an excessivelysmall diameter of lower than 1 μm are used, the particles are buried ina coating liquid, a large amount of fine particles are required to beadded in order to realize a desired gloss value, and sufficient slippingproperties are hard to obtain. When particles having a large particlediameter of more than 10 μm are used, the diameter exceeds the coatingthickness, so that the particles are likely to fall.

The content of the fine particles to be added is determined asappropriate in the range of 0.1 to 60 wt % according to the degree ofthe surface gloss value required in the packaging material and theparticle diameter, the type, and the like of the fine particles to beadded. Irrespective of the type of the fine particles to be used, whenthe content is lower than 0.1 wt %, a gloss value of 30% or lower ishard to realize. Thus, an improvement effect of the molding propertiescannot be sufficiently obtained. On the contrary, when the particles areexcessively contained in a proportion of higher than 60 wt %, there is afear that the gloss value excessively decreases, so that the appearanceis impaired. A preferable range of the content of the fine particles isin the range of 5 to 55 wt % and particularly preferably in the range of20 to 50 wt %. In a case of using silica as the inorganic particles,when the particle diameter and the content are in the upper and lowerlimit range mentioned above, the gloss value is easily controlled in therange of 1 to 30% and particularly in the optimal range of 2 to 10%, andgood slipping properties can be imparted to the surface.

(Outside Adhesive Layer)

An adhesive constituting the adhesive layer (11) includes, but notparticularly limited thereto, a two component curing type urethaneadhesive containing a polyol component and an isocyanate component andthe like, for example. The two component curing type urethane adhesiveis suitably used when bonding by a dry lamination method. The polyolcomponent includes, but not particularly limited thereto, polyesterpolyol, polyether polyol, and the like, for example. The isocyanatecomponent includes, but not particularly limited thereto, diisocyanates,such as TDI (tolylenediisocyanate), HDI (hexamethylenediisocyanate), andMDI (methylenebis(4,1-phenylene)diisocyanate), for example. Thethickness of the adhesive layer (11) is preferably set to 2 μm to 5 μmand particularly preferably set to 3 μm to 4 μm.

In the adhesive layer (11), inorganic or organic antiblocking agents andamide slip agents may be added to the constituent resin described aboveinsofar as the effects of the invention are not impaired.

(Barrier Layer—Metallic Foil—)

The metallic foil forming the barrier layer (4) has a function of givinggas barrier properties for preventing entering of oxygen or moistureinto the molding packaging material (1). The metallic foil includes, butnot particularly limited thereto, aluminum foil, copper foil, and thelike, for example and the aluminum foil is generally used. The thicknessof the metallic foil is preferably 20 μm to 100 μm. Due to the fact thatthe thickness is 20 μm or more, the generation of pinholes in rollingwhen manufacturing the metallic foil can be prevented. Due to the factthat the thickness is 100 μm or lower, stress in bulging and drawforming can be made small, so that the molding properties can beimproved.

In the barrier layer (4), at least to the inside surface (4 a), i.e.,the surface on the side of the sealant layer (3), is subjected tochemical conversion treatment. By subjecting such chemical conversiontreatment to the metallic foil, a corrosion of the surface of themetallic foil caused by contents (an electrolytic solution of a battery,foods, pharmaceuticals, and the like) can be sufficiently prevented. Forexample, the metallic foil is subjected to the chemical conversiontreatment by carrying out the following treatment. More specifically,for example,

1) an aqueous solution containing a mixture of metallic salts ofphosphoric acid, chromic acid, and fluoride,

2) an aqueous solution containing a mixture of phosphoric acid, chromicacid, and fluoride metallic and nonmetallic salts,

3) an aqueous solution containing a mixture of an acrylic resin or/and aphenol resin, phosphoric acid, chromic acid, and a fluoride metallicsalt, and

4) an aqueous solution containing a mixture of an acrylic resin or/and aphenol resin, an phosphate or a phosphoric acid compound, a chromate ora chromic acid compound, and a fluoride metallic salt, are applied tothe surface of the metallic foil subjected to degreasing treatment, andthen dried to thereby form a chemical conversion film.

(Inside Adhesion Resin Layer)

With respect to the inside adhesion resin layer (5) for bonding thebarrier layer (4) and the inside sealant layer (3), the selection of thematerial is particularly important in order to prevent a degradationwith time of the lamination strength caused by an influence of anelectrolytic solution and the like. An adhesive resin having goodadhesiveness at least to both the metallic foil (aluminum) as thebarrier layer (4) and an interface resin of the inside sealant layer (3)is required to use. A specific resin type includes, but not particularlylimited thereto, a resin obtained by performing graft additionmodification or copolymerization of dicarboxylic acids, such as maleicacid, fumaric acid, itaconic acid, and mesaconic acid, dicarboxylic acidanhydrides, such as a maleic acid anhydride, fumaric acid anhydride,itaconic acid anhydride, and mesaconic acid anhydride, carboxyl groupcontaining monomers, such as acrylic acid, methacrylic acid, crotonicacid, and itaconic acid, and the like, with polypropylene, for example.Among the above, a resin obtained by performing graft additionmodification with maleic acid anhydride, acrylic acid, and methacrylicacid is preferably used, and particularly maleic anhydride modifiedpolyolefin resin is preferable. A method for manufacturing the resin isnot particularly limited and a solution method including dissolvingpolypropylene in an organic solvent, and then reacting the solution withacid (maleic acid anhydride and the like) in the presence of a radicalgenerating agent, a melting method including heating and meltingpolypropylene, and then reacting the resultant substance with acid(maleic acid anhydride and the like) in the presence of a radicalgenerating agent, and the like, can be mentioned, for example.

The inside adhesion resin layer (5) is particularly preferablyconstituted by an adhesive composition containing a polyolefin resinhaving a carboxyl group in the chemical structure and a multifunctionalisocyanate compound in order to increase the useful life of thepackaging material by sufficiently securing electrolytic solutionresistance. The adhesion resin layer (5) is usually formed by applyingan adhesive liquid containing a polyolefin resin having a carboxylgroup, a multifunctional isocyanate compound, and an organic solvent tothe barrier layer (4) or/and the inside sealant layer (3), and thendrying the same.

The polyolefin resin having a carboxyl group (hereinafter also sometimesreferred to as a “carboxyl group containing polyolefin resin”) includes,but not particularly limited thereto, a modified polyolefin resinobtained by performing graft polymerization of ethylenic unsaturatedcarboxylic acid or an acid anhydride thereof with polyolefin, acopolymerization resin of an olefin monomer and ethylenic unsaturatedcarboxylic acid, and the like, for example. The polyolefin includes, butnot particularly limited thereto, homopolymers of olefin monomers, suchas ethylene, propylene, and butene, or copolymers of these olefinmonomers, and the like, for example. The ethylenic unsaturatedcarboxylic acid includes, but not particularly limited thereto, acrylicacid, methacrylic acid, maleic acid, fumaric acid, crotonic acid,itaconic acid, and the like, for example. The ethylenic unsaturatedcarboxylic acid may be used singly or in combination of two or morekinds thereof. As the carboxyl group containing polyolefin resin, onewhich dissolves in an organic solvent is preferably used.

Among the above, as the carboxyl group containing polyolefin resin, itis preferable to use a modified polyolefin resin obtained by performinggraft polymerization of ethylenic unsaturated carboxylic acid or an acidanhydride thereof with a homopolymer of propylene or a copolymer ofpropylene and ethylene.

The multifunctional isocyanate compound reacts with the carboxyl groupcontaining polyolefin resin, and acts as a curing agent for curing anadhesive composition. The multifunctional isocyanate compound includes,but not particularly limited thereto, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophoronediisocyanate, isocyanurate modified substances, biuret modifiedsubstances of the diisocyanate compounds, or modified substancesobtained by performing adduct modification of the diisocyanate compoundswith polyhydric alcohols, such as trimethylol propane, and the like, forexample. The multifunctional isocyanate compounds may be used singly orin combination of two or more kinds thereof. As the multifunctionalisocyanate compound, a multifunctional isocyanate compound whichdissolves in an organic solvent is preferably used.

The organic solvents are not particularly limited insofar as the organicsolvents can dissolve or disperse the carboxyl group containingpolyolefin resin. Among the above, organic solvents which can dissolvethe carboxyl group containing polyolefin resin are preferably used. Asthe organic solvents, organic solvents which can be easily volatilizedand removed from the adhesive liquid by heating or the like arepreferably used. Mentioned as the organic solvents which can dissolvethe carboxyl group containing polyolefin resin and can be volatilizedand removed by heating or the like are, for example, but notparticularly limited thereto, aromatic organic solvents such as tolueneand xylene, aliphatic organic solvents such as n-hexane, alicyclicorganic solvents such as cyclohexane and methyl cyclohexane (MCH),ketone organic solvents such as methyl ethyl ketone (MEK), and the like.These organic solvents may be used singly or in combination of two ormore kinds thereof.

In the adhesive liquid or the adhesion resin composition, the equivalentratio [NCO]/[OH] of an isocyanate group of the multifunctionalisocyanate compound to a hydroxyl group constituting the carboxyl groupof the carboxyl group containing polyolefin resin is preferably set to1.0 to 10.0. When the ratio is set in such a range, the adhesivecomposition excellent in the initial adhesion performance can beachieved and a reduction with time in the adhesion strength between themetallic foil layer (4) and the inside sealant layer (3) caused by anelectrolytic solution of a battery can be sufficiently suppressed over alonger period of time, so that the electrolytic solution resistance canbe further increased. The equivalent ratio [NCO]/[OH] is more preferablyset to 1.5 to 9.0 and particularly preferably set to 1.5 to 6.0.

In the adhesive liquid and the adhesive composition, additives, such asa reaction accelerator, a tackifier, and a plasticizer, may becompounded, as required.

The thickness of the adhesion resin layer (5) is preferably set to 1 μmto 10 μm. When the thickness is 1 μm or more, sufficient adhesivestrength can be obtained. When the thickness is 10 μm or lower, thewater vapor barrier properties can also be improved.

The carboxyl group containing polypropylene resin of the adhesion resinlayer (5) may be a single composition or a mixture of two or more kindsof substances different in the melting point.

(Inside Sealant Layer)

The resin constituting the inside sealant layer (3) includes, but notparticularly limited thereto,

1) a random copolymer resin containing propylene and ethylene as acopolymerization component,

2) a copolymer resin containing propylene, ethylene, and butene as acopolymerization component,

3) a block copolymer resin containing propylene and ethylene as acopolymerization component,

4) a propylene homopolymer, and the like for example.

In the copolymer resin of each of 1) to 3) above, an olefinthermoplastic elastomer may be blended.

For the resin of the inside sealant layer (3), it is preferable to use acopolymer resin having a melting point of 130° C. to 160° C. Thecopolymer resin having a melting point of 130° C. to 160° C. refers to aresin having a peak temperature (melting point) measured by a DSC(differential scanning calorimeter) at a temperature elevation rate of20° C./min of 130° C. to 160° C. Due to the fact that the melting pointis 130° C. or higher, sufficient heat resistance can be secured andalso, due to the fact that the melting point is 160° C. or lower,excellent sealing properties can be secured.

Among the resin 1) to the resin 4) above constituting the inside sealantlayer (3), it is preferable to use a copolymer resin containing at leastpropylene and ethylene as a copolymerization component and having an MFRof 1 g/10 min to 15 g/10 min. The MFR (melt flow rate) is a valuemeasured according to JIS K7210-1999 (Condition M). Due to the fact thatthe MFR is 1 g/10 min or more, extrusion lamination can be easilyperformed. Due to the fact that the MFR is 15 g/10 min or lower, thefluidity of the resin in sealing becomes moderate, so that moreexcellent sealing properties can be secured.

The thickness of the inside sealant layer (3) is preferably 10 to 80 μm.Due to the fact that the thickness is 10 μm or more, sufficient sealingstrength can be obtained, and also, due to the fact that the thicknessis 80 μm or lower, a water vapor barrier from the end surface can besufficiently prevented from being damaged. It is a matter of course thatthe inside sealant layer (3) may be constituted by a single layer asmentioned above or a multilayer such as a co-extrusion film ofpolypropylene and one obtained by performing extrusion lamination ofpolypropylene two times. In the latter case, when a polypropylene layerwith high fluidity is disposed on the outside (innermost layer side) ofa polypropylene layer with low fluidity, an extremely reduction in theseal thickness due to an unusual flow of the polypropylene layer insealing can be sufficiently prevented.

In the molding packaging material (1) of the configuration describedabove, the adhesion resin layer (5) is excellent in affinity to both themetallic foil as the barrier layer (4) and the inside sealant layer (3),and therefore the interlayer lamination strength between the layers canbe sufficiently increased. Therefore, when the packaging material (1) ismolded into a battery case, for example, a reduction in the interlayerlamination strength caused by an influence of an electrolytic solutioncan be prevented and a reduction in the interlayer lamination strengthcaused by an influence of a generation of heat and an expansion and acontraction of the packaging material due to a repetition of charge anddischarge can also be prevented, so that sufficient sealing propertiescan be secured.

(Manufacturing Method)

Next, an example of a method for manufacturing the molding packagingmaterial (1) of the invention is described with reference to FIGS. 1 and2.

First, a biaxially oriented polyamide film (2) as the outside substratelayer (2) is bonded to one surface of the metallic foil as the barrierlayer (4) with the adhesive (11) by a dry lamination method, forexample. Furthermore, the matte coat layer (6) containing a twocomponent curing type heat-resistant resin containing a dispersion ofinorganic particles is formed by coating on the biaxially orientedpolyamide film (2).

As the barrier layer (4), a metallic foil in which at least the insidesurface (surface to which a treatment liquid to be used in the followingprocess is applied) (4 a) is subjected to chemical conversion treatmentis used. The metallic foil (4) in which both surfaces are subjected tochemical conversion treatment may also be used.

On the other surface (inside surface) (4 a) of the barrier layer (4),the inside sealant layer (3) is formed through the adhesion resin layer(5) having good adhesiveness to both the metallic foil and the interfaceside resin of the inside sealant layer. Thus, a laminate (30) isobtained (FIG. 1).

Subsequently, a two component curing type resin liquid containing adispersion of inorganic and/or organic fine particles, such as silica,in a heat-resistant resin component in which fluorine is added to theskeleton of a main agent, for example, is applied to the outside surfaceof the outside substrate layer (2) of the laminate (30), and then dried,thereby obtaining the matte coat layer (6) in which the surface glossvalue is controlled in the range of 1 to 30%. A method for applying thetwo component curing type resin liquid for the formation of the mattecoat layer (6) includes, but not particularly limited thereto, a gravureroll method, for example.

Subsequently, the laminate (30) was passed through a heat roll (23)heated to 130° C. to 220° C. in such a manner that the matte coat layer(6) on the outermost surface of the laminate (30) is on the side of theheat roll, thereby obtaining the molding packaging material (1) of theinvention illustrated in FIG. 1 (FIG. 2).

The molding packaging material (1) of the invention is manufactured intoa packaging container body for a battery case, foods, andpharmaceuticals, and the like by molding (bulging, deep draw forming,and the like) into various shapes, such as a rectangular parallelepipedshape with a high molding height. In the battery case, the foodpackaging container, and the pharmaceutical packaging container obtainedby performing such molding, the contents are prevented from enteringbetween the layers of the barrier layer (4) formed with a metallic foiland the inside adhesion resin layer (5). Therefore, when molded into abattery case, for example, a reduction in the lamination strength causedby an influence of an electrolytic solution can be prevented and areduction in the lamination strength caused by an influence of ageneration of heat and an expansion and a contraction of the packagingmaterial due to a repetition of charge and discharge can be prevented,so that favorable sealing performance can be maintained over a longperiod of time.

EXAMPLES

Next, specific Examples of the invention are described but the inventionis not particularly limited to those Examples.

Example 1

A chemical conversion treatment liquid containing polyacrylic acid, atrivalent chromium compound, water, and alcohol was applied to bothsurfaces of a 40 μm thick aluminum foil (4) (substrate layer), thealuminum foil was dried at 180° C., and then chemical conversiontreatment was carried out in such a manner that the chromium adhesionamount was 10 mg/m².

Then, a 15 μm thick biaxially oriented 6 nylon film (2) (outsidesubstrate layer) was dry laminated on one surface of the aluminum foilwith a two component curing type urethane adhesive (11).

Furthermore, a maleic acid modified polypropylene resin (5) (insideadhesive layer) having adhesiveness to both metallic foil andpolypropylene and an ethylene-propylene random copolymer resin (3)having a melting point of 140° C. and an MFR of 7 g/10 min were extrudedand prepared as a laminate film on the other surface (4 a) of thealuminum foil (4) by a T die method in such a manner that the maleicacid modified polypropylene resin layer was 7 μm and theethylene-propylene random copolymer layer was 28 μm.

Subsequently, the laminate film was placed on the chemicalconversion-treated surface of the aluminum foil (4), and then passedthrough a heat roll heated to 150° C., thereby obtaining a laminate(30).

Subsequently, a two component curing type resin composition containing50 wt % of silica having an average particle diameter of 3 μm and acopolymer of tetrafluoroorefin and carboxylic acid vinyl ester wasapplied to the surface of the outside substrate layer with a gravureroll, and then dried to thereby form a matte coat layer (6), whereby amolding packaging material (1) illustrated in FIG. 1 was obtained.

Each composition, each component, and the like of the matte coat layer(6), the inside adhesion resin layer (5), and the inside sealant layer(3) are as shown in Table 1.

In Table 1, the following abbreviated names are used.

Fluorine-added two component curing type resin: Two component curingtype resin composition containing a copolymer of tetrafluoroolefin andcarboxylic acid vinyl ester

m-PP: Maleic acid anhydride modified polypropylene (Modifiedpolypropylene resin obtained by performing graft polymerization ofmaleic acid anhydride with a copolymer of propylene and ethylene)

M-PP: Maleic acid anhydride modified polypropylene (Modifiedpolypropylene resin obtained by performing graft polymerization ofmaleic acid anhydride with a copolymer of propylene and ethylene)

Random PP: Propylene-ethylene random copolymer resin

Block PP: Propylene-ethylene block copolymer resin

Homo PP: Polypropylene resin

Multifunctional isocyanate: Polymer body of hexamethylene diisocyanate(NCO content of 23.1 mass %)

Examples 2 to 7

Various kinds of molding packaging materials were obtained in the samemanner as in Example 1, except changing the component composition of thematte coat layer (6) to various kinds of component compositions.

Example 8

A 15 μm thick biaxially oriented 6 nylon film (2) formed by an inflationmethod was dry laminated on one surface of an aluminum foil (4) (barrierlayer) in which both surfaces were subjected to conversion treatmentwith a two component curing type urethane adhesive (11) in the samemanner as in Example 1.

Subsequently, a 60 μm thick propylene-ethylene random copolymer film (3)(the innermost layer of a sealant layer) was laminated and integrated onthe other surface (4 a) of the aluminum foil (4) by a sandwichlamination method through an extruded resin layer (the outermost layerof the sealant layer) obtained by extruding a maleic anhydride modifiedpolypropylene resin (5) (inside adhesion resin layer) and apropylene-ethylene random copolymer resin having a melting point of 130°C. and an MFR of 20 g/10 min from an extrusion die of an extrusionmachine, and adjusting the thickness to be 20 μm.

Subsequently, a two component curing type heat-resistant resincomposition containing 45 wt % of silica having an average particlediameter of 5 μm, in which fluorine was added to the skeleton of a mainagent, was applied with a gravure roll, and then dried to form a mattecoat layer (6). A molding packaging material (1) was obtained in thesame manner as in Example 1, except the operation above.

Example 9

A 15 μm thick biaxially oriented 6 nylon film (2) formed by an inflationmethod was dry laminated on one surface of an aluminum foil (4)(barrierlayer) in which both surfaces were subjected to conversion treatmentwith a two component curing type urethane adhesive (11) in the samemanner as in Example 1.

Subsequently, an adhesive in which 0.9 g of a polymer body ofhexamethylene diisocyanate (multifunctional isocyanate compound, NCOcontent of 23.1 mass %) was mixed in a solution in which 15 g of maleicacid modified polypropylene (modified polypropylene resin obtained byperforming graft polymerization of maleic anhydride with a copolymer ofpropylene and ethylene, Melting temperature: 77° C., Acid value: 10mgKOH/g) was dissolved in 85 g of a mixed solvent (mixed solvent ofmethyl cyclohexane:methyl ethyl ketone=8 parts by mass:2 parts by mass)in such a manner that the equivalent ratio [NCO]/[OH] was 1.8 wasapplied onto the other surface (4 a) of the aluminum foil (4), and thendried at 80° C. to form a 3 μm thick inside adhesion resin layer (5).Then, an 80 μm thick non-oriented three-layer film (3) containing apropylene-ethylene random copolymer, block polypropylene, and apropylene-ethylene random copolymer (inside sealant layer) shown inTable 1 was dry laminated on the surface of the dried adhesion resinlayer (5). A molding packaging material (1) was obtained in the samemanner as in Example 1, except the operation above.

Example 10

A molding packaging material (1) was obtained in the same manner as inExample 9, except using an adhesion resin shown in Table 1 for theconstituent material of the inside adhesion resin layer (5) and using a80 μm thick non-oriented homopolypropylene film for the sealant layer(3).

Example 11

A molding packaging material (1) was obtained in the same manner as inExample 9, except using an adhesion resin shown in Table 1 for theconstituent material of the inside adhesion resin layer (5) and using an80 μm thick non-oriented two-layer film containing homopolypropylene anda propylene-ethylene random copolymer shown in Table 1 for the sealantlayer (3).

Comparative Example 1

A molding packaging material was obtained in the same manner as inExample 1, except not having the matte coat layer (6).

Comparative Example 2

A molding packaging material was obtained in the same manner as in theadhesion resin layer in Example 9 and the sealant layer in Example 10,except not having the matte coat layer (6).

The melting point mentioned in the description of each Example and eachComparative Example is a melting point measured at a temperatureelevation rate of 20° C./min using an automatic differential scanningcalorimeter (Product number: DSC-60A) manufactured by Shimadzu Corp.

Each molding packaging material obtained as described above wasevaluated for the performance based on the following evaluation methods.The results are shown in Table 1.

TABLE 1 Com- Com- Ex- Ex- Ex- Ex- Ex- Ex- Ex- parative parative Exam-am- am- am- am- am- am- am- Exam- Exam- Exam- Exam- Exam- ple 1 ple 2ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 ple 9 ple 10 ple 11 ple 1 ple 2Matte Heat resistant resin Fluorine- ← ← ← ← ← ← ← ← ← ← coat Solidadded layer fine two particles com- ponent curing type resin Type SilicaSilica Silica Silica Silica Acryl Silica Silica Silica + Silica SilicaAcryl Particle 3 3 3 2 2 2 2 5 5 5 5 dimaeter (μm) content 50 55 42 2818 55 58 45 45 45 45 (wt %) Coating amount (μm) 3 3 3 3 2 3 3 3 3 3 3Surface gloss value (%) 3.5 2 5.5 14 25.2 3.5 3.5 3.5 3.5 3.5 3.5 Ad-Type m-PP ← ← ← ← ← ← ← M-PP + M-PP + M-PP + m-PP M-PP + hesion Multi-Multi- Multi- Multi- resin func- func- func- func- layer tional tionaltional tional iso- iso- iso- iso- cyanate cyanate cyanate cyanateEquivalent ratio — — — — — — — — 1.8 1.8 1.8 — 1.8 [NCO]/[OH] Meltingpoint (° C.) 140 ← ← ← ← ← ← 160 77 85 80 140 77 MFR (g/10 min) 7 ← ← ←← ← ← 8 — — — 7 — Viscosity of adhesive — — — — — — — — 30 25 30 — 30(mPa · S (° C.)) Thickness (μm) 7 ← ← ← ← ← ← 5 3 3 3 7 3 Ex- TypeRandom PP truded Melting point (° C.) 130 resin MFR (g/10 min) 20 layerThickness (μm) 15 Sealant Type Random ← ← ← ← ← ← Random Random HomoHomo Random Homo layer PP PP PP PP PP PP PP Block PP Random Random PP PPMelting point (° C.) 140 ← ← ← ← ← ← 140 140 160 160 140 160 160 140 140MFR (g/10 min) 7 ← ← ← ← ← ← 8 7 7 7 7 7 2 7 7 Thickness (μm) 28 ← ← ← ←← ← 60 12 80 64 28 60 56 16 12 Per- Molding properties ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ × × form- Electrolytic solution ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ × × anceadhesion appearance eval- Lamination strength ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ○ ⊚ ○ ⊚ ⊚uation Electrolytic solution ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ resistanceSealing performance ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ *The viscosity of theadhesion resin is a viscosity measured using a B type rotationalviscometer at 25° C.

<Molding Properties Evaluation Method>

The molding packaging materials were subjected to bulging into arectangular parallelepiped shape of Length of 55 mm×Width of 35 mm×Depthof 8 mm using a bulging machine manufactured by Amada Co., Ltd. (Productnumber: TP-25C-X2), and the molding properties were evaluated based onthe following judgment criteria.

(Judgment Criteria)

-   “⊚” Pinholes were not generated and also cracks were not generated.-   “Δ” Pinholes were slightly generated in a small portion but    substantially hardly generated.-   “×” Pinholes and cracks were generated in corner portions.

<Lamination Strength Evaluation Method>

The molding packaging materials were cut into a 15 mm width to formmeasurement pieces, and the lamination strength (lamination strength ofthe inside adhesion resin layer (5) and the inside sealant layer (3)) ofthe measurement pieces was measured by a tensile test machine under a80° C. atmosphere.

(Judgment Criteria)

-   “⊚” The lamination strength is 5 N/15 mm width or more.-   “∘” The lamination strength is 3 N/15 mm width or more and lower    than 5 N/15 mm width.-   “×” The lamination strength is lower than 3 N/15 mm width.

<Electrolytic Solution Resistance Evaluation Method>

The molding packaging materials were cut into a 15 mm width to formmeasurement pieces, a solution in which lithium hexafluorophosphate wasdissolved in a mixed solvent in which ethylene carbonate and diethylenecarbonate were mixed with a capacity ratio of 1:1 in such a manner thatthe concentration was 1 mol/L and the measurement pieces were placed ina wide-mouth bottle formed with polytetrafluoroethylene, the bottle wasstored in a 85° C. oven for one week, the measurement pieces were takenout, and then the inside adhesion resin layer (5) and the inside sealantlayer (3) were separated at the interface to measure the laminationstrength (adhesion strength) between the layers.

(Judgment Criteria)

-   “⊚” With respect to the measured adhesion strength, the retention    rate is 90% or more based on the initial adhesion strength.-   “∘” With respect to the measured adhesion strength, the retention    rate is 60% or more and lower than 90% based on the initial adhesion    strength.-   “Δ” With respect to the measured adhesion strength, the retention    rate is 30% or more and lower than 60% based on the initial adhesion    strength.-   “×” With respect to the measured adhesion strength, the retention    rate is lower than 30% based on the initial adhesion strength    (including one in which interlayer separation occurred during    immersion).

<Electrolytic Solution Adhesion Appearance Evaluation>

The molding packaging materials were cut into 10 cm×10 cm, 1 cc of asolution in which lithium hexafluorophosphate was dissolved in a mixedsolvent in which ethylene carbonate and diethylene carbonate were mixedwith a capacity ratio of 1:1 in such a manner that the concentration was1 mol/L was added dropwise to the outermost surface of the moldingpackaging materials, and then the appearance was evaluated when thesurface of a portion to which the liquid droplets adhere was rubbed backand forth 10 times using a rubbing implement in which cotton was woundaround a weight with a diameter of 1 cm and a weight of 1 Kg with thewound cotton.

-   “⊚” The appearance did not change even when the portion was rubbed    back and forth 10 times.-   “Δ” The appearance changed when the portion was rubbed back and    forth 5 times.-   “×” The appearance change when the portion was rubbed back and forth    once.

<Sealing Performance Evaluation Method>

A seal separation test was carried out under the conditions of 25° C.and 80° C. using TENSILON RTA-100 manufactured by Orientec Co., Ltd.,and a constant temperature bath TCF-III1-B manufactured by Baldwin,Inc., and then the sealing performance was evaluated. With respect tothe sealing conditions, the sealing was performed for each moldingpackaging material at a sealing width of 5 mm, a sealing pressure of 0.3MPa, a sealing time of 1 second, and a sealing temperature of 160° C.and 180° C. (both surface heating).

(Sealing Performance Judgment Criteria)

-   “⊚” Those having a strength of 30 N/15 mm or more in both a case    where the sealing was carried out at 160° C. and the seal separation    test was carried out at 25° C. and a case where the sealing was    carried out at 180° C. and the seal separation test was carried out    at 80° C.-   “∘” Those having a strength of 25 N/15 mm or more and lower than 30    N/15 mm was obtained in both a case where the sealing was carried    out at 160° C. and the seal separation test was carried out at    25° C. and a case where the sealing was carried out at 180° C. and    the seal separation test was carried out at 80° C.-   “×” Those not falling under the criteria above (poor sealing    performance).

<Gloss Value>

The gloss value was measured at a reflection angle of 60° using a“micro-TRI-gloss-s” manufactured by BYK as a measurement apparatus.

As is clear from the performance evaluation results of Table 1, in themolding packaging materials of Examples 1 to 11 of the invention, thegloss value of the outside surface is controlled to a sufficiently smallvalue, and, as a result, it was able to be confirmed in the molding testthat pinholes and cracks are not generated and the molding propertiesare excellent. It was able to be confirmed that the packaging materialsoriginally achieve sufficient interlayer lamination strength and areexcellent also in electrolytic solution resistance, electrolyticsolution adhesion appearance, and sealing performance.

On the other hand, in the molding packaging materials of ComparativeExamples 1 and 2 not having the matte coat layer, the molding propertieswere inferior.

The present application claims priority of Japanese Unexamined PatentApplication Publication No. 2011-72461, filed on Mar. 29, 2011 and theentire disclosure is a part of the present application.

INDUSTRIAL APPLICABILITY

The molding packaging material according to the invention is suitablyused as a case material of secondary batteries, such as lithium ionbatteries for notebook personal computers, cellular phones, andon-vehicle and fixed type power sources, and also is suitably used as apackaging material for foods, pharmaceuticals, and the like.

DESCRIPTION OF THE REFERENCE NUMERALS

-   1 Molding packaging material-   2 Outside substrate layer (heat-resistant resin layer)-   3 Inside sealant layer (thermoplastic resin)-   4 Barrier layer (metallic foil)-   5 Inside adhesion resin layer-   6 Matte coat layer-   11 Adhesive layer-   23 Heat roll

1. (canceled)
 2. A method for manufacturing a molding packagingmaterial, comprising: a step of subjecting at least one surface of ametallic foil for a barrier layer to chemical conversion treatment; astep of bonding a biaxially oriented polyamide film to the other surfaceof the metallic foil with an outside adhesive to form an outsidesubstrate layer; a step of applying a resin composition in which 0.1 wt% to 60 wt % of a dispersion of inorganic and/or organic solid fineparticles having an average particle diameter of 1 jam to 10 μm iscontained in a two component curing type heat-resistant resin to asurface of the outside substrate layer, and then drying to form a mattecoat layer whose gloss value is controlled to be 1 to 30%; a step offorming an inside adhesion resin layer having adhesiveness to both themetallic foil as the barrier layer and a resin of an inside sealantlayer described later on one chemical conversion-treated surface of themetallic foil; a step of laminating and forming the sealant layercontaining a thermoplastic resin on the inside adhesion resin layer; anda step of heat treating a laminate obtained by the steps above with aheat roll heated to 130° C. to 220° C. in such a manner that the outsidesubstrate layer is on the side of the heat roll.
 3. The method formanufacturing a molding packaging material according to claim 2, whereina resin containing a propylene homopolymer or a copolymer resincontaining at least propylene and ethylene as a copolymerizationcomponent and having a melting point of 130° C. to 160° C. and an MFR of1 to 25 g/10 min is used as the thermoplastic resin of the sealantlayer.
 4. The method for manufacturing a molding packaging materialaccording to claim 2, wherein the inside adhesion resin layer is formedby applying and drying an adhesion resin containing a polyolefin resinhaving a carboxyl group and a multifunctional isocyanate compound andhaving an equivalent ratio [NCO]/[OH] of an isocyanate group of themultifunctional isocyanate compound to a hydroxyl group constituting thecarboxyl group of the polyolefin resin of 1.0 to 10.0.
 5. The method formanufacturing a molding packaging material according to claim 2, whereinthe two component curing type heat-resistant resin includes a copolymerof tetrafluoroolefin and carboxylic acid vinyl ester.